Synthesis of porous oxide ceramics using a soft responsive scaffold

Ceramic materials have significant utility. Developing synthetic protocols that are facile and provide low energy alternatives to traditional methods remains a major driver in materials synthesis. We present here the adaptation of a method recently developed in our group for the synthesis of porous silica using a non-ionic emulsion template. The silicate materials are porous on both the nanometre and micrometre length scales and surface-to-volume ratios may be readily modified by altering the volume fraction of the emulsion template. Switching the silica precursor for an alumina or titania precursor resulted in the formation of porous alumina and titania materials which were prepared as thin films or monoliths. The pores formed in the amorphous alumina materials were ~0.8 μm and ~50 nm, with a primary particle size of 50–100 nm. The titania materials had pores on one length scale only: ~0.8 μm, with a smaller primary particle size of 20–60 nm. As-synthesized materials were investigated using scanning electron microscopy and X-ray diffraction.     

On the inhomogeneous hydration kinetics and stiffness evolution of HNBR‐MgO reactive elastomer composites

Swellable elastomers are widely used in oilfield industry for sealing and zonal isolation applications. These materials need to sustain a large amount of external load after swelling. A newly developed reactive hydrogenated nitrile butadiene rubber (HNBR) based elastomer composite with magnesium oxide (MgO) as filler can swell and stiffen when exposed to water, which makes it ideal for oil field applications. However, both the filler hydration and the stiffness evolution inside this composite material are observed to be highly inhomogeneous even for samples on the length scale of millimeters. To understand this coupled diffusion‐hydration process is critical for applications of these materials with larger length scales. In this work, the hydration kinetics and stiffness evolution of the HNBR‐MgO composite are quantitatively studied on microscopic level. The extent of MgO hydration along the thickness of the sample are measured at the different stage of swelling. These results are used to determine the diffusion coefficient of water inside the composite. The diffusivity increases orders of magnitude after the filler hydration. In addition, the modulus change is non‐proportional to the degree of filler hydration as demonstrated by instrumented grid indentation on the hydrated composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43420.     

Myelinosome Organelles in the Retina of R6/1 Huntington Disease (HD) Mice: Ubiquitous Distribution and Possible Role in Disease Spreading

Visual deficit is one of the complications of Huntington disease (HD), a fatal neurological disorder caused by CAG trinucleotide expansions in the Huntingtin gene, leading to the production of mutant Huntingtin (mHTT) protein. Transgenic HD R6/1 mice expressing human HTT exon1 with 115 CAG repeats recapitulate major features of the human pathology and exhibit a degeneration of the retina. Our aim was to gain insight into the ultrastructure of the pathological HD R6/1 retina by electron microscopy (EM). We show that the HD R6/1 retina is enriched with unusual organelles myelinosomes, produced by retinal neurons and glia. Myelinosomes are present in all nuclear and plexiform layers, in the synaptic terminals of photoreceptors, in the processes of retinal neurons and glial cells, and in the subretinal space. In vitro study shows that myelinosomes secreted by human retinal glial Müller MIO-M1 cells transfected with EGFP-mHTT-exon1 carry EGFP-mHTT-exon1 protein, as revealed by immuno-EM and Western-blotting. Myelinosomes loaded with mHTT-exon1 are incorporated by naive neuronal/neuroblastoma SH-SY5Y cells. This results in the emergence of mHTT-exon1 in recipient cells. This process is blocked by membrane fusion inhibitor MDL 28170. Conclusion: Incorporation of myelinosomes carrying mHTT-exon1 in recipient cells may contribute to HD spreading in the retina. Exploring ocular fluids for myelinosome presence could bring an additional biomarker for HD diagnostics.     

Photocatalytic Hydrogen Production and Carbon Dioxide Reduction Catalyzed by an Artificial Cobalt Hemoprotein

The covalent insertion of a cobalt heme into the cavity of an artificial protein named alpha Rep (αRep) leads to an artificial cobalt hemoprotein that is active as a catalyst not only for the photo-induced production of H₂, but also for the reduction of CO₂ in a neutral aqueous solution. This new artificial metalloenzyme has been purified and characterized by Matrix Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS), circular dichroism, and UltraViolet–Visible spectroscopy. Using theoretical experiments, the structure of this biohybrid and the positioning of the residues near the metal complex were examined, which made it possible to complete the coordination of the cobalt ion by an axial glutamine Gln283 ligand. While the Co(III)–porphyrin catalyst alone showed weak catalytic activity for both reactions, 10 times more H₂ and four times more CO₂ were produced when the Co(III)–porphyrin complex was buried in the hydrophobic cavity of the protein. This study thus provides a solid basis for further improvement of these biohybrids using well-designed modifications of the second and outer coordination sphere by site-directed mutagenesis of the host protein.     

Systematic testing and formal verification to validate reactive programs

The use of systematic testing and formal verification in the validation of reactive systems implemented in synchronous languages is illustrated. Systematic testing and formal verification are two techniques for checking the consistency between a program and its specification. The approach to validation is through specification: two system views are developed in addition to the program, a behavioural specification for systematic testing and a logical specification for formal verification. Pursuing both activities, reactive programs can be validated both more efficiently (in terms of costs) and more effectively (in terms of confidence in correctness). This principle is demonstrated here using the well known lift example.     

Environmentally controlled emulsion electrospinning for the encapsulation of temperature-sensitive compounds

The introduction of highly volatile fragrances within polymeric nano-scaled fibers is a promising route for efficient and simple encapsulation of temperature-sensitive materials. This work describes the investigation of selected parameters influencing the electrospinning of emulsions of poly(vinyl alcohol) (PVA) and (R)-(+) limonene or hexadecane. Thereby the influence of environmental parameters such as temperature and relative humidity on the fiber structure and encapsulation efficiency (EE) of the fragrance is demonstrated. For that purpose, the electrospinning process was carried out in a climatic cabin in which temperature and relative humidity were controlled. Studied temperatures ranged from 8 to 24 °C and relative humidity varied between 55 and 85 %. The influence of temperature was dependent on the PVA concentration in the emulsion. The relative humidity influenced both the obtained fiber morphology and fragrance EE to a higher extent than the temperature due to the hydrophilic nature of the PVA. This study is of importance when considering the use of emulsion electrospinning for encapsulation purposes.     

Disulfide Bond Substitution by Directed Evolution in an Engineered Binding Protein

Breaking ties : The antitumour protein, neocarzinostatin (NCS), is one of the few drug‐carrying proteins used in human therapeutics. However, the presence of disulfide bonds limits this protein's potential development for many applications. This study describes a generic directed‐evolution approach starting from NCS‐3.24 (shown in the figure complexed with two testosterone molecules) to engineer stable disulfide‐free NCS variants suitable for a variety of purposes, including intracellular applications.

     

Argon Attenuates Multiorgan Failure in Relation with HMGB1 Inhibition

Argon inhalation attenuates multiorgan failure (MOF) after experimental ischemic injury. We hypothesized that this protection could involve decreased High Mobility Group Box 1 (HMGB1) systemic release. We investigated this issue in an animal model of MOF induced by aortic cross-clamping. Anesthetized rabbits were submitted to supra-coeliac aortic cross-clamping for 30 min, followed by 300 min of reperfusion. They were randomly divided into three groups (n = 7/group). The Control group inhaled nitrogen (70%) and oxygen (30%). The Argon group was exposed to a mixture of argon (70%) and oxygen (30%). The last group inhaled nitrogen/oxygen (70/30%) with an administration of the HMGB1 inhibitor glycyrrhizin (4 mg/kg i.v.) 5 min before aortic unclamping. At the end of follow-up, cardiac output was significantly higher in Argon and Glycyrrhizin vs. Control (60 ± 4 and 49 ± 4 vs. 33 ± 8 mL/kg/min, respectively). Metabolic acidosis was attenuated in Argon and Glycyrrhizin vs. Control, along with reduced amount of norepinephrine to reverse arterial hypotension. This was associated with reduced interleukin-6 and HMGB1 plasma concentration in Argon and Glycyrrhizin vs. Control. End-organ damages were also attenuated in the liver and kidney in Argon and Glycyrrhizin vs. Control, respectively. Argon inhalation reduced HMGB1 blood level after experimental aortic cross-clamping and provided similar benefits to direct HMGB1 inhibition.